EP0157108B1 - Procédé de fabrication de copolymères d'éthylène et de comonomères renfermant des groupes carboxyliques dans un réacteur à deux zones de pression supérieure à 500 bars - Google Patents

Procédé de fabrication de copolymères d'éthylène et de comonomères renfermant des groupes carboxyliques dans un réacteur à deux zones de pression supérieure à 500 bars Download PDF

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Publication number
EP0157108B1
EP0157108B1 EP85101056A EP85101056A EP0157108B1 EP 0157108 B1 EP0157108 B1 EP 0157108B1 EP 85101056 A EP85101056 A EP 85101056A EP 85101056 A EP85101056 A EP 85101056A EP 0157108 B1 EP0157108 B1 EP 0157108B1
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EP
European Patent Office
Prior art keywords
ethylene
mol
reactor
beispiel
moles
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EP85101056A
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German (de)
English (en)
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EP0157108A1 (fr
Inventor
Werner Dr. Metzger
Franz Dr. Brandstetter
Klaus Dr. Boettcher
Klaus Dr. Pfleger
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BASF SE
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BASF SE
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Priority to AT85101056T priority Critical patent/ATE40705T1/de
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/02—Ethene

Definitions

  • the invention relates to a process for the preparation of copolymers of ethylene with 1.0 to 2.5 moles, based on 100 moles of ethylene, of copolymerized C 3 - to C 6 -alkenecarboxylic acids in a continuously operated tubular polymerization system at pressures of 500 to 5000 bar and temperatures of 50 to 450 ° C in the presence of radical decomposed polymerization initiators, in which the polymerization system at its inlet point and at the same time at a second point behind the inlet point along the polymerization system, where the reaction temperature has exceeded a maximum, a mixture of ethylene, the Alkenecarboxylic acid, optionally another monomer copolymerizable with ethylene, initiator and optionally regulator.
  • Terpolymers of ethylene with monomers containing carboxyl groups and a further monomer copolymerizable with ethylene are also described, for example, in British Patents 1298732, 1 196185 and 1468228.
  • DE-A-1 952 693 mentions the possibility of producing ethylene copolymers with comonomers containing carboxyl groups or with other comonomers in a single-zone reactor.
  • the object of the present invention was therefore to find an improved process which enables the copolymerization of ethylene with comonomers containing carboxyl groups in a tubular polymerization system at high conversions.
  • more than 50 mol% of the alkenecarboxylic acid is metered in at the second feed point.
  • a method is also preferred in which less than 0.28 mol of alkenecarboxylic acid, based on 100 mol of ethylene, is metered in at the inlet point.
  • Copolymers of ethylene with C 3 -C 6 -alkenecarboxylic acids are understood to mean the copolymers of ethylene which can be prepared at the specified temperature and pressure ratios. A temperature range from 150 to 350 ° C. and a pressure range from 150 to 3000 bar are preferred.
  • copolymers of ethylene with C 3 - to C 6 -alkenecarboxylic acids encompass copolymers with contents of copolymerized comonomers containing carboxyl groups of 1.0 to 2.5 mol, based on 100 mol of ethylene. If another Co.
  • Copolymerizable with ethylene If monomer is additionally used, the content of additionally copolymerized comonomer is below 7 mol, based on 100 mol of ethylene, preferably in the range from 1 to 4 mol.
  • the following are particularly suitable as C 3 -C 6 -alkenecarboxylic acids: acrylic acid, methacrylic acid, itaconic acid , Aconitic acid, maleic acid, citraconic acid. Acrylic acid and methacrylic acid are particularly suitable.
  • esters of (meth) acrylic acid of alcohols having 1 to 8 carbon atoms are suitable; Vinylcarbonklareester, particularly Vinylester of C, - to C a- alkanecarboxylic acids; Esters of ethylenically unsaturated dicarboxylic acids, in particular mono- or diesters of maleic acid and fumaric acid; Amides of monoethylenically unsaturated carboxylic acids, especially acrylic and methacrylic acid amide; as well as N-mono- and N-dialkylamides of acrylic and methacrylic acid: monoethylenically unsaturated ketones or carbon monoxide.
  • Esters of (meth) acrylic acid of alcohols having C 1 -C 8 carbon atoms are particularly preferred. Methyl, ethyl and n-butyl acrylate are particularly
  • the ethylene is copolymerized with the C 3 -C 6 -alkenecarboxylic acids and optionally with the other comonomers copolymerizable with ethylene in the presence of free radical initiators.
  • Free radical polymerization initiators are understood to mean those catalysts which are also used for the homopolymerization of ethylene under high pressure.
  • Oxygen is suitable, for example, expediently in amounts of 2 to 100 mol ppm, based on the ethylene to be polymerized.
  • Peroxides and other radical formers, as well as mixtures of peroxides with different decomposition points and hydroperoxides and mixtures of oxygen and peroxides and / or hydroperoxides are also suitable.
  • peroxides and hydroperoxides examples are: tert-butyl peroxipivalate, di-tert-butyl peroxide, tert-butyl hydroperoxide, tert-butyl perbenzoate or dilauroyl peroxide.
  • Free radical polymerization initiators are also to be understood as meaning compounds such as azoisobutyric acids. Mixtures of oxygen and one or more peroxides can also be used.
  • Suitable regulators are, for example, hydrogen, ketones, alcohols, ethers or normal and branched hydrocarbons. Propylene, butene or propionaldehyde are preferably used.
  • the copolymerization is generally carried out in the absence of a solvent.
  • an inert solvent such as benzene, mineral oils or other inert solvents, in which the polymerization initiators are dissolved, can be neglected compared to the other starting materials. If only oxygen is used as the polymerization initiator, any solvent can be omitted.
  • Tubular reactors are tubular polymerization vessels whose length: diameter ratio of the pressure-resistant tubes is in the range from 10,000 to 60,000: 1.
  • Information on ethylene high-pressure polymerization processes using tubular reactors can be found, for example, in “ U llmann's Enzyclopadie der technical chemistry”, (1980), 4th edition, vol. 19, pages 167-178, Verlag Chemie GmbH, D-6940 Weinheim .
  • the gaseous mixture of ethylene, C 1 -C 4 -alkenecarboxylic acid, if appropriate a further monomer copolymerizable with ethylene, initiator and, if appropriate, controller is now at the inlet point and at the same time at a second point behind the inlet point along the tube reactor in the direction of flow polymerizing ethylene, where the reaction temperature has exceeded a maximum, is fed to the reactor according to the procedure of U.S. Patents 3,725,378 and 4,076,919 cited above.
  • the inlet point is generally understood to mean the beginning of the tubular reactor.
  • the main stream is fed in at the beginning of the reactor, the secondary stream is fed to the reactor in a known manner near the second point at which a temperature maximum is formed. By this measure, the reaction of the known two-zone tube reactor is obtained.
  • a mixture of ethylene, alkenecarboxylic acid, optionally a further monomer copolymerizable with ethylene, initiator and optionally regulator is introduced at the inlet point and at a second feed point along the reactor, the proportion of carboxyl-containing monomer at the inlet point of the reactor being at a maximum 0.3 moles, preferably less than 0.28 moles, based on 100 moles of ethylene.
  • the rest of the C 3 -C 6 -alkenecarboxylic acid is then metered in at the second feed point along the reactor.
  • a process in which more than 50 mol% of the alkenecarboxylic acid is metered into the reactor at the second feed point is also preferred.
  • a further monomer copolymerizable with ethylene is also possible.
  • a mixture of ethylene, 0.1 to 0.25 mol of acrylic acid and 0.1 to 0.3 mol of n-butyl acrylate, based on 100 mol of ethylene, is carried out at the inlet point and at the second feed point 0.4 to 0.8 mol of acrylic acid and 0.55 to 0.8 mol of n-butyl acrylate to the reactor.
  • the dosing of the alkenecarboxylic acids according to the invention to the first and second zones of the two-zone reactor leads to copolymers of ethylene with comonomers containing carboxyl groups and having good properties at high conversions.
  • the copolymerization of the ethylene with the comonomers was carried out in all cases in a tubular reactor.
  • the ethylene was mixed with the specified amount of oxygen and the necessary amount of regulator in two separate gas streams with a ratio of 1: 1 and compressed to the reaction pressure.
  • one of the gas strands was fed to the inlet point of the reactor and the other at a second gas feed point approximately after 1: 3 of the entire reactor length, after the reaction had developed at a maximum temperature in the first reactor part and the temperature of the mixture had already returned was decaying, fed to the reactor.
  • two reaction zones were formed in the tubular reactor (two-zone reactor).
  • the length and diameter ratio of the reactor in both reaction zones was about 10,000.
  • the tube walls were cooled from the outside with water.
  • the amount of comonomers required for the copolymerization was distributed over the gas train to the first and second reaction zones.
  • Comparative experiment 2 When carrying out comparative experiment 1, only the first reaction zone (single-zone reactor) was used. Comparative experiment 2 was carried out in an autoclave (volume 15 l; length / diameter ratio 2.5).
  • the resulting copolymer was separated in a known manner from the unreacted monomers in the separators downstream of the reactor.
  • the pressure at the second feed point was 2200 bar.
  • the reaction mixture reached a temperature of 300 ° C. in the first part of the reactor and a temperature of 270 ° C. after the second feed point.
  • the amount of regulator was measured so that a melt index of 7 (example 1, 2) or 3 g / 10 min (example 3, measured according to DIN 53 735 at 190 ° C. and 2.16 kp) was established.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymerisation Methods In General (AREA)

Claims (3)

1. Procédé de préparation de copolymères d'éthylène avec 1,0 à 2,5 moles, pour 100 moles d'éthylène, d'un acide alcènecarboxylique en C3-C6 copolymérisable, dans un système de polymérisation tubulaire exploité en continu à des pressions de 500 à 5000 bars et des températures de 50 à 450°C en présence d'initiateurs de polymérisation à décomposition radicalaire, procédé dans lequel on envoie dans le système de polymérisation en son point d'entrée et simultanément en un deuxième point en aval du point d'entrée le long du système de polymérisation, où la température de réaction a dépassé un maximum, un mélange d'éthylène, de l'acide alcènecarboxylique, éventuellement d'un autre monomère copolymérisable avec l'éthylène, d'initiateur et éventuellement de régulateur, caractérisé en ce que, au point d'entrée du système de polymérisation, la quantité d'acide alcènecarboxylique se monte au plus à 0,3 mole pour 100 moles d'éthylène et le reste sera introduit de façon dosée au deuxième point d'admission.
2. Procédé selon la revendication 1, caractérisé en ce que plus de 50% en moles de l'acide alcènecarboxylique seront introduits de façon dosée au deuxième point d'admission du réacteur.
3. Procédé selon la revendication 1, caractérisé en ce que moins de 0,28 mole d'acide alcènecarboxylique sera introduit de façon dosée au point d'entrée.
EP85101056A 1984-02-10 1985-02-01 Procédé de fabrication de copolymères d'éthylène et de comonomères renfermant des groupes carboxyliques dans un réacteur à deux zones de pression supérieure à 500 bars Expired EP0157108B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT85101056T ATE40705T1 (de) 1984-02-10 1985-02-01 Verfahren zur herstellung von copolymerisaten des ethylens mit carboxylgruppenhaltigen comonomeren in einem 2-zonen-reaktor bei druecken oberhalb 500 bar.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3404742 1984-02-10
DE19843404742 DE3404742A1 (de) 1984-02-10 1984-02-10 Verfahren zur herstellung von copolymerisaten des ethylens mit carboxylgruppenhaltigen comonomeren in einem 2-zonen-reaktor bei druecken oberhalb 500 bar

Publications (2)

Publication Number Publication Date
EP0157108A1 EP0157108A1 (fr) 1985-10-09
EP0157108B1 true EP0157108B1 (fr) 1989-02-08

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EP85101056A Expired EP0157108B1 (fr) 1984-02-10 1985-02-01 Procédé de fabrication de copolymères d'éthylène et de comonomères renfermant des groupes carboxyliques dans un réacteur à deux zones de pression supérieure à 500 bars

Country Status (6)

Country Link
US (1) US4579918A (fr)
EP (1) EP0157108B1 (fr)
JP (1) JPS60184511A (fr)
AT (1) ATE40705T1 (fr)
CA (1) CA1250998A (fr)
DE (2) DE3404742A1 (fr)

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DE3615562A1 (de) * 1986-05-09 1987-11-12 Basf Ag Verfahren zur herstellung von copolymerisaten des ethylens mit acrylsaeureestern in einem roehrenreaktor bei druecken oberhalb 500 bar
DE3615563A1 (de) * 1986-05-09 1987-11-12 Basf Ag Verfahren zur herstellung von copolymerisaten des ethylens mit vinylestern in einem roehrenreaktor bei druecken oberhalb 500 bar
DE3844047A1 (de) * 1988-12-28 1990-07-05 Basf Ag Copolymerisate aus ethylen mit alkencarbonsaeuren und/oder alkencarbonsaeurederivaten
US5542677A (en) * 1994-12-20 1996-08-06 Lisco, Inc. Golf ball cover compositions
US5902869A (en) * 1996-03-22 1999-05-11 E. I. Du Pont De Nemours And Company Thermally stable ethylene/acid copolymers
US6160059A (en) 1996-07-26 2000-12-12 Cook Composites And Polymers Co. Bulk polymerization process for preparing solid acrylic resin
DE19647564A1 (de) * 1996-11-18 1998-05-20 Basf Ag Verfahren zur Herstellung von Ethylen(Meth)acrylsäure-Copolymeren
AU1278199A (en) 1997-10-31 1999-05-24 Cognis Corporation Continuous bulk polymerization process
DE19754555A1 (de) * 1997-12-09 1999-06-24 Clariant Gmbh Verfahren zur Herstellung von Ethylen-Mischpolymerisaten und deren Verwendung als Zusatz zu Mineralöl und Mineralöldestillaten
DE19829399A1 (de) * 1998-07-01 2000-02-03 Buna Sow Leuna Olefinverb Gmbh Verfahren zur Herstellung von Ethylenhomo- und Ethylencopolymerisaten niederer Dichte
US7021337B2 (en) * 2004-02-27 2006-04-04 Markham Allen R Plumbing test plug and method
US7156755B2 (en) 2005-01-26 2007-01-02 Callaway Golf Company Golf ball with thermoplastic material
US7175543B2 (en) * 2005-01-26 2007-02-13 Callaway Golf Company Golf ball and thermoplastic material
US7312267B2 (en) 2005-02-23 2007-12-25 Callaway Golf Company Golf ball and thermoplastic material
US7612134B2 (en) 2005-02-23 2009-11-03 Callaway Golf Company Golf ball and thermoplastic material
US7612135B2 (en) 2006-02-17 2009-11-03 Callaway Golf Company Golf ball and thermoplastic material

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Also Published As

Publication number Publication date
ATE40705T1 (de) 1989-02-15
DE3404742A1 (de) 1985-08-14
JPS60184511A (ja) 1985-09-20
EP0157108A1 (fr) 1985-10-09
DE3568171D1 (en) 1989-03-16
CA1250998A (fr) 1989-03-07
US4579918A (en) 1986-04-01

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